For the preparation of higher performance Li-ion batteries, we fabricated a binder-free and selfsupported hybrid nanofiber composed of ZnO nanoparticle-decorated core/shell carbon nanofibers (CNFs) by single-nozzle electrospinning of polyvinylpyrrolidone, polyacrylonitrile and zinc acetate dihydrate. After calcination, the hybrid nanofiber can directly serve as binder-free and self-supported anode for Li-ion batteries, which exhibits high capability (723 mA h g(-1) at 100 mA g(-1)) and good cycling stability. The CNFs in crisscross structure with good conductivity and strength ensure the fast transportation of electrons and Li ions. In addition, the ca. 2.0 nm amorphous carbon layers on the surface of ZnO nanoparticles can suppress the volume expansion of ZnO in the insertion/extraction of Li ions and improve the cycling stability of ZnO/CNFs, while do not inhibit the transportation of Li ions. These encouraging results suggest a simple and effective method to obtain binder-free and selfsupported anode material for Li-ion batteries. (C) 2017 Elsevier B.V. All rights reserved.